CN115109547B - Synthesis method and application of terpene-based polyacrylamide capable of being used as hot melt adhesive - Google Patents

Abstract

The invention belongs to the technical field of biomass macromolecule preparation, and particularly relates to a synthetic method and application of terpene-based polyacrylamide capable of serving as a hot melt adhesive. Synthesis of acryl tetrahydrolinalool: evenly mixing tetrahydrolinalool and acrylonitrile according to a certain proportion, slowly dropwise adding a catalyst and deionized water, and synthesizing the tetrahydrolinalool by a Ritter reaction at the temperature of 0-25 ℃ to synthesize the tetrahydrolinalool of the acryl, wherein the tetrahydrolinalool of the acryl is synthesized by the method: dissolving the obtained acryloyl tetrahydrolinalool in dimethylbenzene, adding a free radical initiator, and carrying out free radical polymerization to obtain the polyacrylic tetrahydrolinalool. The invention can rapidly synthesize a great amount of novel biomass vinyl monomer based on a simple Ritter reaction, has a glass transition temperature of 31.2 ℃, can be used as a novel biomass hot melt adhesive, has good bonding performance on glass, ceramics, paper, plastics, wood, metal and the like, and the bonded metal sheet can bear the weight of 25kg of water.

Description

Synthesis method and application of terpene-based polyacrylamide capable of being used as hot melt adhesive

Technical Field

The invention belongs to the technical field of biomass macromolecule preparation, and particularly relates to a synthetic method and application of terpene-based polyacrylamide capable of serving as a hot melt adhesive.

Background

In 1907, human beings synthesized the first synthetic polymer phenolic resin, and a number of low-cost, durable and safe synthetic polymers have been widely used in industrial and agricultural production and daily life. However synthetic polymers are exposed to more and more problems in use: the self-repairing, degradation and recycling of the thermoplastic resin are difficult, and particularly the thermoplastic resin cannot be processed again after the thermosetting resin is molded. These urgent problems lead to almost all polymeric materials being used only linearly throughout their life cycle: production, use and discarding, and simultaneously, the high polymer material is changed into an environment killer. At present, the "plastic-limiting" rule for limiting and reducing the use of the high polymer material cannot solve the problem of "white pollution" of the high polymer material from the source.

9 months 2020, china proposed at the United nations university: the carbon peak is striven for before 2030 and the carbon neutralization is striven for before 2060, which is a broad and profound systematic transformation of economy and society. The development of sustainable polymers will provide important support for achieving this goal. The conversion of renewable natural small molecules into macromolecules with specific functions is a research hotspot of sustainable macromolecules at present.

The hot melt adhesive resin used in large quantity at present is formed by copolymerizing ethylene and vinyl acetate under high temperature and high pressure, namely EVA resin. EVA is synthesized and prepared based on traditional petroleum fossil resources through a complex chemical process, and a large amount of carbon dioxide is discharged in the synthetic processing stage, so that the realization of carbon peak and carbon neutralization is not facilitated.

Terpenes are a generic term for a series of terpenoids, which are olefinic compounds of the formula of an integer multiple of isoprene. Terpenes are a class of natural source hydrocarbons that are widely found in plants and are available from many plants, particularly conifers. It is the main component of resin and turpentine derived from resin. According to recent studies, in addition to the fact that terpenoids are present in large amounts in plants, a large amount of terpenoids have been extracted from marine organisms. The total number of known terpenoids is statistically over 22000. Therefore, the development of terpene macromolecules is of great significance.

The synthesis of sustainable biomass polymer materials based on renewable terpene compounds to replace the existing plastic elastomers has a great pushing effect on reducing carbon emissions in China and even the world.

Disclosure of Invention

Aiming at the defects existing in the prior art, the invention provides a synthetic method and application of terpene-based polyacrylamide which can be used as a hot melt adhesive, and a renewable terpene compound is utilized to synthesize a sustainable high polymer hot melt adhesive to replace the existing petroleum-based hot melt adhesive so as to solve the problem that the existing petroleum-based high polymer hot melt adhesive material is not feasible and sustainable.

In order to achieve the above purpose, the present invention adopts the following technical scheme: a method for synthesizing terpene-based polyacrylamide which can be used as a hot melt adhesive,

(1) Synthesis of acryl tetrahydrolinalool:

evenly mixing tetrahydrolinalool and acrylonitrile according to a certain proportion, slowly dropwise adding a catalyst and deionized water, and synthesizing the acryloyltetrahydrolinalool through a Ritter reaction at the temperature of 0-25 ℃ with the following reaction formula:

(2) Synthesis of Polyacryloyl tetrahydrolinalool:

dissolving the acryloyl tetrahydrolinalool obtained in the step (1) in dimethylbenzene, adding a free radical initiator, and carrying out free radical polymerization to obtain the polyacrylic tetrahydrolinalool, wherein the reaction formula is as follows:

further, the specific preparation steps include:

(1) Mixing tetrahydrolinalool and acrylonitrile, slowly dripping catalyst and deionized water, wherein the reaction temperature is 0-25 ℃ and the reaction time is 4-12 hours; after the reaction is finished, using sodium hydroxide to neutralize the catalyst, using methylene dichloride to dissolve the obtained product, performing rotary evaporation concentration, and performing vacuum drying at room temperature for 48 hours to obtain colorless transparent viscous oily liquid;

(2) Dissolving the acryloyl tetrahydrolinalool obtained in the step (1) in dimethylbenzene, adding a free radical initiator, carrying out free radical polymerization for 10-24 hours at 50-80 ℃ to obtain the polyacrylic tetrahydrolinalool, carrying out rotary evaporation concentration after the polymerization is finished, precipitating a polymer by using diethyl ether, and carrying out vacuum drying at room temperature for 48 hours to obtain the off-white hard waxy solid.

Further, the method comprises the steps of,

in the step (1), the mixing ratio of tetrahydrolinalool to acrylonitrile is 1:1-1:2.

Further, the method comprises the steps of,

in the step (1), the catalyst is one of concentrated sulfuric acid, trifluoromethanesulfonic acid or Amberlyst-15.

Further, the method comprises the steps of,

in the step (1), the molar ratio of the catalyst to the acrylonitrile is 1:1.

Further, the method comprises the steps of,

in the step (2), the free radical initiator is an azo initiator or a peroxy initiator.

Further, the method comprises the steps of,

the azo initiator is Azobisisobutyronitrile (AIBN) or Azobisisoheptonitrile (ABVN).

Further, the peroxy initiator is dibenzoyl peroxide (BPO).

An application of a synthetic method of terpene-based polyacrylamide which can be used as a hot melt adhesive,

the terpene-based polyacrylamide is used for synthesizing a biomass hot melt adhesive with sustainable polymers, has good bonding performance on glass, ceramics, paper, plastics, wood and metal, and a metal sheet with the bonding area of 10mm multiplied by 10mm can bear the weight of 25kg of water.

The synthetic method and the application of the terpene-based polyacrylamide which can be used as the hot melt adhesive have the advantages that: tetrahydrolinalool is a widely used terpene spice, has the advantages of wide sources and reproducibility, can rapidly synthesize a brand new biomass vinyl monomer in large quantity based on a simple Ritter reaction, has the glass transition temperature of 31.2 ℃, can be used as a novel biomass hot melt adhesive, has good bonding performance on glass, ceramics, paper, plastics, wood, metal and the like, and can bear the weight of 25kg of water for bonded metal sheets.

Drawings

FIG. 1 is a hydrogen nuclear magnetic pattern of acryl tetrahydrolinalool amine in the example;

FIG. 2 is a carbon nuclear magnetic pattern of acryl tetrahydrolinalool amine in the example;

FIG. 3 is a hydrogen nuclear magnetic pattern of polyacrylic tetrahydrolinalool amine in the examples;

FIG. 4 is a gel permeation chromatogram of polyacrylic tetrahydrolinalool amine in the examples;

FIG. 5 is a photograph showing the adhesion of polyacrylic tetrahydrolinalool amine to glass in the examples;

FIG. 6 is a photograph showing the adhesion of polyacrylic tetrahydrolinalool to ceramic in the examples;

FIG. 7 is a photograph showing the adhesion of polyacrylic tetrahydrolinalool to paper in the examples;

FIG. 8 is a photograph showing the adhesion of polyacrylic tetrahydrolinalool to plastic in the examples;

FIG. 9 is a photograph showing adhesion of polyacrylic tetrahydrolinalool amine to metal in the examples;

fig. 10 is a photograph of a 25Kg water drum carried by a metal sheet bonded together with polyacrylic tetrahydrolinalool amine in the examples.

Detailed Description

The following description of the embodiments is provided in conjunction with the accompanying drawings.

The reagents and apparatus in the examples below were conventional experimental reagents and apparatus.

Example 1:

15.83g of tetrahydrolinalool and 6.36g of acrylonitrile are weighed into a 250mL single-neck flask, and placed into an ice water bath at 0 ℃ under intense stirring by magnetic stirring; subsequently, 11.8g of concentrated sulfuric acid (98%) was weighed and diluted to 80%, and slowly added dropwise to the above mixture, and the reaction was continued at room temperature for 8 hours after completion of the addition. Slowly dropwise adding 100mL of 8.8% sodium hydroxide solution into the reaction system, then adding 120mL of dichloromethane into a flask, vigorously stirring, pouring the mixed solution into a separating funnel, standing for layering, flowing out a lower organic phase, concentrating by rotary evaporation, and drying in a vacuum oven at room temperature for 48 hours;

10.5g of the obtained product was weighed into a 100mL single-necked flask, 82mg of azobisisobutyronitrile was added, and dissolved with 50mL of xylene, and after bubbling nitrogen for 30 minutes, the mixture was sealed and placed into an oil bath at 65℃for reaction for 12 hours. After the reaction was completed, the mixture was concentrated by rotary evaporation, and the polymer was precipitated with diethyl ether and dried in a vacuum oven at room temperature for 48 hours.

FIG. 1 is a hydrogen nuclear magnetic pattern of acrylamido tetrahydrolinalool; FIG. 2 is a carbon nuclear magnetic pattern of acryloyltetrahydrolinalool; FIG. 3 is a hydrogen nuclear magnetic pattern of polyacrylic tetrahydrolinalool; FIG. 4 is a gel permeation chromatogram of polyacrylic tetrahydrolinalool amine.

The application of the synthetic method of the terpene-based polyacrylamide which can be used as the hot melt adhesive is that the terpene-based polyacrylamide is used for synthesizing sustainable high molecular biomass hot melt adhesive, has good bonding performance on glass, ceramics, paper, plastics, wood and metal, and a metal sheet with the bonding area of 10mm multiplied by 10mm can bear the weight of 25kg of water.

FIG. 5 is a photograph of the bond of polyacrylic tetrahydrolinalool amine to glass; FIG. 6 is a photograph of the adhesion of polyacrylic tetrahydrolinalool to ceramic; FIG. 7 is a photograph showing the adhesion of polyacrylic tetrahydrolinalool to paper; FIG. 8 is a photograph of the adhesion of polyacrylic tetrahydrolinalool to plastic; FIG. 9 is a photograph of a bond of polyacrylic tetrahydrolinalool amine to a metal; fig. 10 is a photograph of a 25Kg water drum carried by a metal sheet bonded together with polyacrylic tetrahydrolinalool.

Example 2:

the same as in example 1, except that trifluoromethanesulfonic acid was used as the catalyst, 18.0g of sodium hydroxide was added in an amount of 4.5g.

Example 3:

the difference is that the catalyst used is Amberlyst15 solid acid, as in example 1. The catalyst fixes the acid on the microsphere, can be reused, and does not need to be neutralized by sodium hydroxide. The post-treatment steps are simple. The reaction mixture was dissolved in dichloromethane, filtered, concentrated by rotary evaporation and dried in vacuo for 48 hours.

Example 4:

the same as in example 1, except that azobisisoheptonitrile was used as the initiator and 125mg by mass was added.

Example 5:

the same as in example 1, except that benzoyl peroxide was used as initiator, 121mg by mass was added and the polymerization temperature was 80 ℃.

Example 6:

the same as in example 1, except that the mass of the initiator added was 41mg.

Example 7:

the same as in example 4, except that the mass of the initiator added was 63mg.

Example 8:

the difference was that the mass of initiator added was 60mg as in example 5.

The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the essence of the present invention are intended to be included within the scope of the present invention.

Claims (9)

1. A synthetic method of terpene-based polyacrylamide capable of being used as a hot melt adhesive is characterized by comprising the following steps of:

(1) Synthesis of acryl tetrahydrolinalool:

evenly mixing tetrahydrolinalool and acrylonitrile according to a certain proportion, slowly dropwise adding a catalyst and deionized water, and synthesizing the acryloyltetrahydrolinalool through a Ritter reaction at the temperature of 0-25 ℃ with the following reaction formula:

(2) Synthesis of Polyacryloyl tetrahydrolinalool:

dissolving the acryloyl tetrahydrolinalool obtained in the step (1) in dimethylbenzene, adding a free radical initiator, and carrying out free radical polymerization to obtain the polyacrylic tetrahydrolinalool, wherein the reaction formula is as follows:

2. the method for synthesizing a terpene-based polyacrylamide as a hot melt adhesive according to claim 1, wherein the specific preparation steps comprise:

(1) Mixing tetrahydrolinalool and acrylonitrile, slowly dripping catalyst and deionized water, wherein the reaction temperature is 0-25 ℃ and the reaction time is 4-12 hours; after the reaction is finished, using sodium hydroxide to neutralize the catalyst, using methylene dichloride to dissolve the obtained product, performing rotary evaporation concentration, and performing vacuum drying at room temperature for 48 hours to obtain colorless transparent viscous oily liquid;

(2) Dissolving the acryloyl tetrahydrolinalool obtained in the step (1) in dimethylbenzene, adding a free radical initiator, carrying out free radical polymerization for 10-24 hours at 50-80 ℃ to obtain the polyacrylic tetrahydrolinalool, carrying out rotary evaporation concentration after the polymerization is finished, precipitating a polymer by using diethyl ether, and carrying out vacuum drying at room temperature for 48 hours to obtain the off-white hard waxy solid.

3. The method for synthesizing terpene-based polyacrylamide as a hot melt adhesive according to any one of claims 1 or 2, wherein:

in the step (1), the mixing ratio of tetrahydrolinalool to acrylonitrile is 1:1-1:2.

4. The method for synthesizing terpene-based polyacrylamide as a hot melt adhesive according to any one of claims 1 or 2, wherein the method comprises the steps of:

in the step (1), the catalyst is one of concentrated sulfuric acid, trifluoromethanesulfonic acid or Amberlyst-15.

5. The method for synthesizing a terpene-based polyacrylamide as a hot melt adhesive according to any one of claim 1 or 2, wherein,

in the step (1), the molar ratio of the catalyst to the acrylonitrile is 1:1.

6. The method for synthesizing a terpene-based polyacrylamide as a hot melt adhesive according to any one of claim 1 or 2, wherein,

in the step (2), the free radical initiator is an azo initiator or a peroxy initiator.

7. The method for synthesizing a terpene-based polyacrylamide as a hot melt adhesive according to claim 6, wherein,

the azo initiator is Azobisisobutyronitrile (AIBN) or Azobisisoheptonitrile (ABVN).

8. The method for synthesizing a terpene-based polyacrylamide as a hot melt adhesive according to claim 6, wherein,

the peroxy initiator is dibenzoyl peroxide (BPO).

9. A process for the synthesis of a terpene-based polyacrylamide as a hot melt adhesive according to any one of the claims 1 to 8,

the terpene-based polyacrylamide is used for synthesizing a biomass hot melt adhesive with sustainable polymers, has good bonding performance on glass, ceramics, paper, plastics, wood and metal, and a metal sheet with the bonding area of 10mm multiplied by 10mm can bear the weight of 25kg of water.

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